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United States Patent "U " ICC
3,026,307
Patented Mar. 20, 1962
2
1
solution of the alkylated benzene solvent and methyl
3,026,307
CONTINUOUS SOLUTION POLYMERIZATION
OF METHYL METHACRYLATE
William F. Gorham, Berkeley Heights, and Denys F.
Brandon, Newark, N.J., assignors to Union Carbide
Corporation, a corporation of New York
methacrylate is maintained at a temperature between
about 135° C. to about 170° C. to form polymethyl meth
acrylate in amounts constituting between 25 percent to
about 55 percent by weight of the reaction mixture.
Thereafter, a portion of the reaction mixture can be con
No Drawing. Filed July 5, 1956, Ser. No. 595,871
6 Claims. (Cl. 260—89.5)
tinuously withdrawn while adding additional amounts of
the solution of methyl methacrylate to the ?rst heating
solution polymerization of methyl methacrylate‘ in cumene
and related alkylated benzene solvents.
about 55 percent by weight. The removed portion of the
reaction mixture is then devolatilized, preferably by heat
The polymerization of methyl methacrylate is generally
ing in a second heating zone at a temperature between
zone at a rate such that the polymethyl methacrylate con
This invention relates to a process for the continuous 10 tent of the reaction is maintained between about 25 and
about 160° C. and 300° C. and the substantially devola
believed to be a free-radical type reaction involving the
consecutive addition of monomer to a growing polymer 15 tilized polymethyl methacrylate continuously discharged.
‘In this manner of operation, continuous production of
chain. The polymerization can be initiated either by
polymethyl methacrylate of a controlled molecular weight
thermal action or by the use of a free radical catalyst.
Heretofore, batch methods of polymerizing methyl meth
is possible at a rate of about two to four pounds of
acrylate have been most widely accepted for the com
polymer per hour per gallon of reaction volume.
The solution of methyl methacrylate monomer and the
alkylated benzene solvent used in this process should
contain from about one to three parts by weight of methyl
methacrylate monomer per part of the solvent for best
mercial production of polymethyl methacrylate. Accept 20
able and economical continuous processes for production
of usable polymethyl methacrylate resin have, heretofore,
not been known.
results, and more preferably about two to three parts of
Methyl methacrylate polymers generally are character
ized by having an unusually high clarity, are quite stable, 25 methyl methacrylate monomer per part of solvent. If
desired, a polymerization catalyst can also be present in
and well suited to casting, molding, and extruding opera
this solution, for the methyl methacrylate readily poly
tion. Polymers considered most useful for such applica
tions are generally presumed to have average molecular
merizes either with or without bene?t of a catalyst. Free
weights of between 20,000 and 200,000, and correspond
radical'catalysts, for example, benzoyl peroxide, p-men
usable polymers have not‘ been altogether desirable. ‘Bulk
polymerization methods, for example, have been found to
by weight per hundred parts of methyl methacrylate
ing reduced viscosities in chloroform of 0.4- to about 1.0, 30 thane hydroperoxide, bisazodiisobutyronitrile, and cumene
hydroperoxide, have been found to provide excellent
measured as a 0.2 percent solution at 25° C.
results. Amounts of from about 0.0 to about 0.4 part
Polymerization methods for the production of such
monomer provide good results. When using acatalyst in
be undesirable as the polymerization is autocatalytic in 35 ‘this process, We prefer amounts of from about 0.05 to
about 025 part by weight per hundred parts of monomer.
nature and as such is unacceptable for continuous pro
While not desiring to be bound by any particular theory
duction methods. The lack of control over ‘the rate of
of reaction, it is'believed that the alkylated benzene sol
polymerization, particularly after‘ about 15-25 percent re
vents used in this process serve as chain transfer agents
action has taken" place, has hindered exploitation of this
method for continuous polymerization. Molecular 40 in the polymerization. Alkylated benzene solvents hav
WeightS‘Of the polymers produced by the bulk'polymeriza- .
tion method are generally presumed to be between about
ing at least one alkyl group attached to the benzene ring
through a secondary carbon atom or at least two alkyl
200,000 and 1,000,000. The molecular weight of such
products is generally so high that the products have little
groups other than methyl attached to the benzene ring
through primary carbon atoms to the benzene ring can
be employed as the chain transfer solvent. The solvent
should also have a boiling point between 150° C. and
250° C. in order to be completely removed in the second
heating zone of this process. Cumene is the preferred
commercial use.
Batch suspension methods are most
commonly employed in industrial applications. While
the products of suspension processes have good properties
and the process is controllable, the process is not readily
‘adaptable to continuous methods and is relatively expen
sive. This has kept the cost of polymethyl‘methacrylate
high in relation to the cost of other polymeric materials.
A satisfactory continuous process for producing such
products would be highly desirable.
Solvent polymerization methods have heretofore been
little more than of a theoretical interest.
chain transfer solvent for use in this process, although
other alkylated benzenes such as isopropyl toluene, iso
propyl ethyl-benzene, diisopropyl benzene, ‘diethyl ben
zene, triethyl benzene, and the like are suitable. Cumene
is preferred because of the ease of reaction and control
achieved, and the ease of removal in the second heating
In some cases, 55 Z0116.
in the operation of this process, precise control over
solvent polymerization has given products of unexpectedly
high molecular weight in polymerization reactions which
the average molecular weight of the ?nal polymer can
be achieved. Wehave'found that this control is achieved
were dii?cult to control. 'Heretofore, no solvent poly
by precise control over (a) the monomer/solvent ratio,
merization process has, been found to be so controllable
as to lend itself to commercial applications, let alone 60 (b) ‘percent catalyst, (c) reaction temperature, and '(d)
reactor polymer solids content. For instance, by increas
incontinuous processes.
~
‘ing the monomer/cumene ratio and holding all other fac~
According to the .present invention, We have found
tors constant, the average molecular weight of the poly
that methyl methacrylate polymer of a usable and pre
mer increases. If the vpercent catalyst is increased, with
dictable molecular weight can be consistently and con
.trollably produced in a process which includes the steps 65 all other factors constant, the average molecular weight
of the polymer decreases. It the reaction temperaturein
of forming a solution of methyl methacrylate in an alkyl
creases
and all other factors are constant, the molecular
ated'benzene solvent, heating the solution‘in- an enclosed
heating zone to a polymerization temperature of at least
135° C. for a period sufficient to polymerize a portion of
Weight also decreases. If instead the amount of reactor
solids is increased with other factors constant, the molecu
Best operation of this invention is secured when the
temperature at about 160° C., the catalyst at 0.15 part by
the methyl methacrylate and subsequently removing the 70 lar weight of the polymer decreases.
Inillustration of these features, by holding the reaction
solvent and unreacted monomer.
,
3,026,307
3
4
weight per hundred parts of monomer, and reactor solids
at 48 percent, increasing the monomer-curnene ratio from
about 70/30 to 80/ 20 increases reduced viscosity of the
polymer produced from about 0.51 to about 0.65. If in
strand contains only a slight amount of such materials,
e.g. usually less than 5.0 percent. The temperature, pres
sure, residence time, and size of the second chamber can
stead the monomer to cumene ratio is maintained at
70/30 and the catalyst concentration is increased to about
percent or lower. Means other than milling the polymer
0.25 part per hundred parts of monomer, the reduced vis
v'c‘osity of the polymer decreases from about 0.51 to about
all be varied to achieve volatile matter to as low as 1.5
mass can be used to remove the volatile matter, for in
stance, kneading in a vacuum kneader, drying in thin
sheets in a vacuum drier or even precipitation of the
0.40. By maintaining the original catalyst concentration
polymer in a non-solvent.
at about 0.15 part per hundred parts of monomer and in 10
In continuous operation of this process, it is desirable
creasing the reaction temperature to about 170° C., re
to condense the solvent and monomer removed in this
duced viscosity of the polymer will decrease from about
devolatilization step and reuse or recycle them in the
0.51 to about 0.40. If instead, the reactor solids are in
process. Thus by dissolving additional methyl methacry
creased from about 48 percent to about 55 percent, with
late monomer in the condensed volatile mixture up to
all other factors at their original level, the reduced vis 15 original strength, economical operation is secured, with
cosity of the polymer will decrease from about 0.51 to
only slight losses of solvent.
about 0.40.
The polymeric solids after removal from the second
The process is preferably initiated by ?lling the reactor
heating zone should be substantially devolatilized, that is,
with the methyl methacrylate monomer-cumene mixture,
containing about 5.0 percent or less of solvent and un
adding the catalyst if such is to be used, and heating the 20 reacted monomer, and preferably about 1.5 percent or
mixture to the reaction temperature. It is necessary that
the mixture be maintained in the ?rst heating zone at
between ‘about 135° C. to about 170° C., and preferably
between about 155° C. and 165° C. until the amounts of
polymethyl methacrylate in the reaction mixture is at
less. If reduced pressures are used to promote devolatili
zation, the mass will have to be extruded or otherwise me
chanically removed from the chamber at a rate substan
tially equivalent to the rate of addition of the methyl
methacrylate monomer if continuous operation at opti
least 25 percent and not over 55 percent. Superatmos
mum ef?ciency is to be achieved.
pheric pressures within the range of 15 to 100 p.s.i.g. can
The polymethyl methacrylate produced by this process
be employed to secure the desired reaction conditions.
possesses excellent clarity and all desirable properties of
commercial polymethyl methacrylate. The average mo
When the amount of polymeric solids in the reaction is
'within 25 and 55 percent and preferably about 50 per 30 lecular weight of the polymers of this invention can range
cent, a portion of the reaction mixture is continuously
from about 20,000 to about 80,000. For practical pur
poses, we prefer the reduced viscosity method for deter
withdrawn to the second heating zone, and additional
mining molecular weight, with reduced viscosity deter
‘methyl methacrylate monomer-cumene mixture continu
mined by dissolving 0.2 gram of the polymeric product
ously added to the reaction. For continuous operation
over long periods of time, it is preferred that the rate of 35 in 100 grams of chloroform and the viscosity measured
at 25° C. These products have reduced viscosities rang
removal of the reaction mixture and rate of addition of
ing between 0.4 and about 0.8, which are presumed to
the methyl methacrylate monomer-curriene mixture should
correspond to average molecular weights of the polymers
be adjusted so that the polymer solids content in the re
of about 20,000 and about 60,000 to 80,000, respective
action mixture is maintained within the range of 25 to 55
40 ly, the average molecular weight increasing as a function
percent by weight of the reaction mixture.
of the reduced viscosity. The products are further char
The amount of polymeric solids in the reaction mixture
acterized by having A.S.T.M. standard heat distortion
can be directly determined from a sample of the reaction
mixture by precipitation of the polymer in excess meth
temperatures of between about 70° C. and 90° C., the
anol, ?ltering, drying, and weighing the precipitate. In
temperature depending primarily upon whether a plasticiz
continuous operation under steady state conditions, the
polymer solids content is determined by dividing product
rate per hour by total feed rate per hour.
er is present in the product.
If a plasticizer is to be employed in the product, we
have found it advantageous to add it during the working
in the second heating chamber. Being substantially non
The second heating zone is necessary in the operation
of this invention in order to remove the volatile matter, 50 volatile at these temperatures, addition during the mill
i.e. the cumene and unreacted monomer, from the poly
meric solids. This chamber can be operated at a temper
ature within the range of about 160° C. to 300° C. The
optimum temperature selected is dependent upon the resi
ing produces a homogeneous mixture of the plasticizer
in the polymer.
This process allows for e?icient operation on any scale
to continuously produce polymethyl methacrylate resins
dence time in this chamber with both factors so selected 65 of controlled molecular weights.
that substantially all of the volatile matter is removed
The process even on a
large scale is economical and allows for precise control
over the molecular weight and possesses all the advan
from the polymer in this zone. In this process we prefer
tages the continuous operation has over batch operation.
a temperature of about 200° C. at reduced pressures of
This process is ideally suited to the continuous polymer
about 50-100 mm. Hg pressure. However, other temper
atures within this range can be used, and with pressures 60 ization equipment described in U.S. Patents 2,496,653
and 2,614,910.
ranging from 1 mm. Hg up to 760 mm. Hg.
The following examples are illustrative. All parts are
Inasmuch as the removed portion of the reaction mix
parts by weight.
ture contains between about 25 and 55 percent polymer
Example 1
solids and is quite viscous, it is necessary to mechanically
work the mass while removing the volatile matter, prefer 65
A mixture consisting of 65 parts of methyl methacry
ably in an oxygen-free atmosphere. Best operation of
late dissolved in 35 parts of cumene was added to a one
our process is achieved by milling the portion of the
gallon jacketed reactor and heated. The temperature was
reaction mixture removed in this second heating zone for
slowly raised to 160° C. over a 2 hour period, and main
a total residence time of one to ten minutes, in a vacuum
tained at 90 p.s.i.g. pressure at this temperature for four
mill such as described in the patent to Marshall, U.S. 70 more hours, at which point the reaction mixture con
2,434,707, issued January 20, 1948. During this period
of heating and mastication in the Marshall mill, :1 given
sample of material is devolatilized of the solvent and any
unreacted methyl methacrylate monomer. The polymer
tained 26-28 percent polymer solids as determined by
precipitation of the polymer from a sample of the reac
tion mixture, ?ltering, drying, and weighing the polymer.
Part of the reaction mixture was continuously removed
discharged from the second heating zone as a very viscous 75 from the reactor at a rate of about 2.5 pounds per hour
3,026,307
6
heated with agitation for six hours until the temperature
through a back pressure valve set at 90 p.s.i.g. to the sec
ond heating chamber, and an amount of the initial 65/35
rose to 160° C. at a pressure of 40 p.s.i.g. and these con
amount of reaction mixture removed was continuously
ditions maintained for four hours. After this period, the
reaction mixture contained 54-56 percent solids. Part of
added to the reaction mixture to maintain a constant
volume in the reactor and a constant solids content of
of about 21 pounds per hour and replenished with an
about 27 percent. The volatile material in the removed
portion was removed by continuous milling of the poly
mer-containing mixture in the second heating chamber
equivalent amount of the initial 75/25 methyl methacry
late mixture containing the catalyst. The removed por
tion was fed to a heated vacuum milling chamber con
ing speeds which gave substantial mastication of the vis
with dibutyl sebacate as a plasticizer. The plasticizer was
added to the milling chamber at a rate of about 315 grams
methyl methacrylate-cumene mixture equivalent to the
the reaction mixture was continuously removed at a rate
consisting of a vacuum milling chamber similar to that 10 sisting of an enlarged version of the previously described
equipment, and milled at 200° C. at 50 mm. Hg pressure
described in US. Patent 2,434,707 to Marshall using mill
cous mass.
The milling was conducted at 200° C. at 50
per hour so as to maintain about a 6 percent concentra
mm. Hg pressure until the methanol-soluble content, i.e.
cumene and unreacted monomer, in the polymer was less 15 tion of plasticizer in the product. The polymer was ex
truded from the milling chamber at a‘ rate of about 11.5
than 1.5 percent. A total residence time in the milling
pounds per hour, having a methanol-soluble content of
chamber of about one to ten minutes achieved the de
7-7.5 percent which consisted of the 6 percent plasticizer
volatilization. ;
The polymer was continuously discharged from the
and 1 to 11/2 percent residual solvent and monomer. The
Operation in this manner was conducted for 100 hours,
A mixture consisting of 70 parts of methyl methacry
late, 30 parts of cumene and 0.105 p-art of benzoyl per
milling chamber as a viscous strand at a rate of about 20 polymer had a reduced viscosity of 0.66 to 0.68 in chloro
form at 25° C. and a ?ow time of 140-180 seconds to
0.7 pound per hour, was air cooled and stretched about
travel 1.5 inches in a ?ow tester having a 1/8 inch bore
200 percent and cut into 1/8 inch lengths convenient for
under 1000 p.s.i. at 160° C.
subsequent molding or extruding operations. The poly
Operation in this manner was conducted for 50 hours,
mer had a methanol-soluble content of less than about
1.5 percent and a reduced viscosity of 0.70 in chloroform 25 producing 575 pounds of usable polymethyl methacrylate.
at 25° C.
Example 4
producing 70 lbs. of usable polymethyl methacrylate.
Example 2
30
A mixture consisting of 70 parts of methyl methacry
oxide was added to a one gallon jacketed reactor as in
Example 1, and heated.
The temperature was slowly
increased to 160° C. over a four hour period and main
late, 30 parts of cumene and 0.07 part of p-menthane
tained at that temperature for an additional four hours
hydroperoxide was added to a one gallon jacketed reac
at a pressure of 90 p.s.i.g. At the end of this period, the
tor and heated. The temperature was slowly increased
total polymer solids in the reaction mixture was about
35
to 160° C. over a four hour period, and the temperature
48 percent as determined by the previously described
maintained at that level for four hours at 90 p.s.i.g. pres‘
method. Part of the reaction mixture was continuously
sure, after which the polymer solids in the mixture was
removed at a rate of about 6.3 pounds per hour through
about 44-46 percent as determined in the manner de
a back pressure valve set at 90 p.s.i.g. to a heated vac
scribed in Example 1. Part of the reaction mixture was
uum milling chamber as in Example 1. An amount of
40
continuously removed at a rate of about ?ve pounds per
the initial feed mixture, at a rate equivalent to that re
hour through a back pressure valve to a second heated
moved, was continuously added to the reaction mixture
chamber as in Example 1.
to maintain constant volume and constant polymer solids
An amount of the initial feed mixture at a rate equiv
in the reaction mixture of about 48 percent. The part
alent to that removed was continuously added to the re
of ‘the reaction mixture which was removed was con
action mixture to maintain a constant volume and con 45 tinuously milled in the milling chamber as described in
stant polymer solids in the reaction mixture of about 45
percent. The part of the reaction mixture removed was
continuously milled in the heated milling chamber as de
scribed in Example 1 at 200° C. and 50 mm. Hg pres
Example 1 at 200° C. and 50 mm. Hg pressure for a
total residence time of about one to ?ve minutes. The
plasticizer, dioctyl phthalate, was added to the milling
chamber at a rate of about 75 grams per hour so as to
sure for a total residence time of one to ten minutes while 50 maintain about 6 percent by weight of plasticizer in the
being mixed with dioctyl phthalate as a plasticizer. The
amount of dioctyl phthalate added was regulated at
about 62 grains per hour so that the ?nal product would
product. The cumene and unreacted methyl methacrylate
were volatilized in the milling chamber and recovered,
and the devolatilized product was continuously dis
contain about 6 percent by weight of the plasticizer. The
charged from the milling chamber as a viscous strand at
cumene and unreacted methyl methacrylate were volati 55 a rate of about 2.8 pounds per hour, stretched 100 per
lized in the milling chamber, and the plasticized, devolati
cent, and cut into 1/8 inch lengths, convenient for han
lized product was continuously discharged as a viscous
dling. The polymer had a methanol-soluble content of
strand at a rate of about 2.3 pounds per hour. The
about 7.0 percent, consisting of six percent plasticizer
strand was air cooled, stretched about 200 percent, and
and one percent monomer and cumene. The polymer had
cut into 1A; inch segments for molding or extruding.
60 a reduced viscosity of 0.52 in chloroform at 25° C.
The polymethyl methacrylate produced had a methanol
Operation in this manner was conducted for 20 hours,
insoluble content of 92.5-93 percent, the soluble com
producing 56 pounds of usable polymethyl methacrylate.
ponents comprising 6 percent dioctyl phthalate and about
1.5 percent residual cumene and monomer.
It had a re
Example 5
A mixture consisting of 65 parts of methyl methacry
duced viscosity of 0.52 in chloroform at 25° C., and a 65
late, 35 parts of cumene, and 0.13 part of cumene hydro
?ow time of 75-125 seconds for traveling 11/2 inches in
a 1/8” bore tester at 1000 p.s.i. at 160° C.
Operation in this manner was conducted for 40 hours,
peroxide was added to a one gallon jacketed reactor as
in Example 1 and heated. The temperature was gradual
ly increased to 135° C. over a four hour period and main
producing 92 pounds of usable polymethyl methacrylate.
70 tained at that level for four more hours at 50 p.s.i.g.
Example 3
pressure. At the end of this period, the total polymer
A mixture of 75 parts of methyl methacrylate, 25 parts
of cumene and 0.056 part of cumene hydroperoxide was
fed to a ten gallon autoclave which was maintained about
solids in the reaction mixture amounted to about 30 per
cent. Part of the reaction mixture was continuously
withdrawn. at a rate of about 1.4 lbs. per hour, and an
70 percent full during operation. The mixture was slowly 75 equivalent amount of the initial feed mixture at a rate
3,026,307
7
equivalent to that removed was continuously added to
135° C. to about 170° C., a solution of methyl methacry
the reaction mixture to maintain constant volume and con
late and cumene, containing from about one to about
stant polymer solids in the reaction mixture of about 30
ercent. The portion of the reaction mixture removed
three parts by weight of methyl methacrylate per part of
was continuously milled in a milling chamber as de
scribed in Example 1 at 200° C. and 50 mm. Hg pressure
for a total residence time of about one to ?ve minutes.
cent by weight, while continuously removing a portion of
The plasticizer, dibutyl sebacate, was added to the milling
cumene, at a rate sufficient to maintain polymer solids in
the reaction mixture between about 25 and about 55 per
the reactor contents into a second heated chamber main
tained at a temperature between about 160° C. and 300°
chamber at a rate of about 62 grams per hour so as to
C., removing substantially all of the volatile content, and
maintain a concentration of about 10 percent by weight 10 recovering the solid polymethyl methacrylate thus pro
of plasticizer in the product. The cumene and unreacted
duced.
methyl methacrylate were volatilized in the milling cham
3. A process as de?ned by claim 2 wherein a free-radical
ber and recovered, and the devolatilized product was con
polymerization catalyst is employed.
tinuously discharged from the milling chamber at a rate
4. A process for the continuous polymerization of
of about 1.4 pounds per hour, stretched 200 percent, and
methyl methacrylate to high molecular weight solid poly
cut into 1/s inch lengths convenient for molding or extrud~
mers which includes the steps of heating a solution of
ing operations. The polymer had a methanol-soluble
methyl methacrylate monomer dissolved in cumene in
content of about 13 percent consisting of 10 percent
amounts of between about one to about three parts by
plasticizer and 3 percent cumene and unreacted monomer,
weight of methyl methacrylate monomer per part of
and had a reduced viscosity of 0.89 in chloroform at
cumene to a temperature between about 135° C. to about
25° C.
170° C. to form a polymethyl methacrylate solids con
Operation in this manner was conducted for 10 hours,
tent in the mixture between about 25 to about 55 percent,
producing 14 pounds of usable polymethyl methacrylate.
thereafter continuously withdrawing a portion of the re
What is claimed is:
action mixture to a second heating zone and continuously
1. A process for the continuous polymerization of
adding methyl methacrylate monomer dissolved in cumene
methyl methacrylate to high molecular weight solid poly
to the ?rst heating zone at a rate such that the solids
mers which includes the steps of continuously adding to
content of the reactor is maintained between about 25 to
a reactor maintained at a temperature between about
about 55 percent, heating the removed portion in the
135° C. and about 170° C., a solution of methyl meth
second heating zone at a temperature between about 160°
acrylate and an alkylated benzene solvent selected from 30 C. to about 300° C., removing substantially all volatile
the class consisting of alkylated benzenes having at least
matter and recovering the solid polymethyl methacrylate
thus produced.
one alkyl group attached to the benzene ring through a
secondary carbon atom and alkylated benzenes having at
5. A process according to claim 4 wherein the second
least two alkyl groups other than methyl attached to the
heating zone is a heated milling chamber maintained
benzene ring through primary carbon atoms, said solvent 35 under reduced pressures.
having a boiling point between 150° C. and 250° C.,
6. A process according to claim 4 wherein a free-radical
said solution containing from one to three parts by weight
of methyl methacrylate per part of solvent, at a rate
su?icient to maintain polymer solids in the reaction mix
ture between about 25 and about 55 percent by weight, 40
while continuously removing a portion of the reaction
contents into a second heated chamber maintained at a
temperature between about 160° C. and 300° C., remov
ing substantially all of the volatile content in the said
removed portion and recovering the solid polymethyl 45
methacrylate thus produced.
2. A process for the continuous polymerizaiton of
methyl methacrylate to high molecular weight solid poly
mers which includes the steps of continuously adding to
a reactor maintained at a temperature of between about 50
polymerization catalyst is employed.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,577,677
2,752,387
2,769,804
2,777,832
Crouch _______________ __ Dec. 4,
Rehberg _____________ __ June 26,
Hanson _______________ __ Nov. 6,
Mallison _____________ __ Jan. 15,
1951
1956
1956
1957
OTHER REFERENCES
Basu et al.: Proc. Roy. Soc. (London), 202A, 485~498
( 1950).
Schildknecht et al.: “High Polymers,” vol. X, pp. 178-9,
lnterscience Pub., Inc., New York (1956).